Method of defoliating plants



ray-

United States Patent V O METHOD OF DEFOLIATING PLANTS Lewis Edward Goyette, Richmond, Va., assignor to Virginia-Carolina Chemical Corporation, Richmond, Va., a corporation of Virginia No Drawing. Filed June 9, 1958, Ser. No. 740,545

Claims. (Cl. 71-23) cotton, the trialkyl phosphorotrithioites are useful for defoliation of other plants. I have further found that there are other organic compounds containing sulfur and trivalent phosphorus, phosphorotrithioites, which are also excellent defoliants, and that there are other organic compounds containing sulfur, trivalent phosphorus, and oxygen, phosphorodithioites and phosphoromonothioites, that are also excellent defoliants. By organic compounds I mean compounds which in addition to the above named elements also contain hydrocarbon chains and/or hydrocarbon rings and may contain other groups substituted in the hydrocarbon chain or hydrocarbon ring.

Any substance which can duplicate the effect of a light frost on a plant is commonly called a defoliating agent. The effect of the application of such a material is equivalent to a light frost causing the formation of abscission layers of cells across the petiole bases of the leaves of the plants. The result is a premature leaf drop.

By far the largest use at present for detoliants is in the defoliation of cotton plants. However, there is also interest in defoliants for such plants as roses, hydrangeas, many types of huh and shade trees, and for other field grown crops such as soybeans. Because of the wide interest in and use of defoliants for cotton the majority of my work has been with cotton; however, I have found that the compounds useful in my method of defoliating cotton are also useful in defoliating other plants, and my invention is concerned with a method of defoliating all types of plants which normally have an annual leaf-drop. However, as stated above, most of my work has been primarily concerned with cotton.

On normal cotton plants which are not treated with defoliating agents, the bolls on the lower branches open first while the bolls on the upper branches continue to open slowly over a period of as long as two months from the time when picking of the lower bolls is desirable. The majority of the leaves remain attached to the plant and cause green stains on the cotton when mechanical cotton pickers are employed. In addition, the leaves high on the plant shade the lower bolls from sunlight and air resulting in excessive boll rot. At times, 15% of the .cotton crop has been lost because of this boll rot. Without the use of defoliating agents, numerous hand pickings are necessary to prevent boll rot and staining.

I have discovered that the foliage of cotton plants can be treated with many types of phosphorothioite compounds with the result that the leaves are shed and the bolls open uniformly. Thus, the entire crop may be 2,955,803 Fatented Get. 11, 1960 machine harvested at one time and also at an earlier date than normal because of the quick loss of leaves. By phosphorothioite compounds, I mean compounds as previously described which contain trivalent phosphorus and sulfur, and in some instances, oxygen.

The amount of defoliant to be applied will depend upon the kind of vegetation to be defoliated and the density thereof, as well as the choice of defoliant compound. As is illustrated in the following examples, emulsions containing as little as 0.03% by weight of the active ingredients have been used effectively. My compounds have been found to be effective when applied to normal cotton stands at rates varying from 1.00 to 10 lbs. per acre, but it is to be understood that these figures do not represent either maximum or minimum limits.

The defoliant is applied to cotton usually when the bolls are from 35 to 40 days old, but this may vary with the season and climate.

Improved, very efiicient defoliant compositions are obtained when oil-in-water emulsions of solutions of my compounds in oil are prepared. The word oil is used here to designate any liquid which is a solvent for the phosphorothioites of my invention and is insoluble in water, such as xylene, kerosene, diesel oil, benzene, carbon tetrachloride, ether, heptane, heavy mineral oils, and water insoluble solutions of Water-soluble liquids in water-insoluble liquids such as a solution of ethyl alcohol in kerosene. The emu sions may be obtained by first dissolving the phosphorothioite in the oil and then mixing the resulting solution with water in the presence of an emulsifying agent. In actual commercial sale and application, the defoliant compounds are dissolved in the oil solvent and the emulsifier is added to the solution. In the field this mixture of active ingredient, oil and emulsifier is mixed with water before actual application to the cotton plant. Any of the many methods of spray application may be employed.

Emulsifying agents customarily used in the art for the preparation of oil-in-Water emulsions are operable in the practice of my invention, e.g., ionic or non-ionic emulsifying or dispersing agents such as the long-chain alkylbenzene-sulfonates or polyglycol ethers. Such emulsifying agents are normally employed in only very small concentrations, for example, in a quantity up to about 0.3% by weight based on the weight of the emulsion. However, it is possible to use any amount of emulsifying agent up to a quantity which would be detrimental to the cotton plant. Some emulsifiers show phytotoxic reactions when used on living plants. Concentrations of emulsifier up to about 5% by weight do not normally damage healthy cotton plants. Such emulsifiers do not affect the chemical stability or defoliating activity of the phosphorothioites.

While the compounds of my invention are advantageously used as defoliants when formulated into oilin-water emulsions, they may also be dissolved in organic solvents or so-called oils as mentioned above, and such solutions applied directly onto the cotton plants. In formulations such as the latter a wetting agent is sometimes required. They may also be mixed with solid carriers such as clay, talc, pumice, and bentonite and then dusted onto the cotton plants. The compounds may also be mixed and applied with liquid or solid agricultural pesticides such as insecticides and/or fungicides. While all of these methods of application are operable, the oil-in-water emulsions and the solutions of the compounds in oil are preferred. The emulsions tend to adhere easily to the plant foliage and are very readily applied by conventional spray methods. The preferred methods of application require less of the active ingre useful if the cotton is ,to be hand picked. The bolls open uniformly and with the. leaves gone morercotton-can be harvested withone picking;

In the foregoing paragraphs, the uses and methods of application of defoliants on cotton have been discussed. However, as will be seen in some of the following tables and examples, the compounds of my invention are also useful as defoliants on a number of other plantssueh as ro'ses, hydrangeas, and plum, peach, Siberian elm, pear, sand cherry, and ash trees. 7 V

.As was previously stated, the compounds of utility in my invention are phosphorothioites, and are defined by the following generic formulas:

where R is hydrogen or a lower-alkylor substituted loweralkyl group, and Ar is an aryl or substituted aryl group. The upper limit of the size of the alkyl, group in Formulas '1, 2, 3, 5, 6, and 7 has not been determined, but there is good reason to believe that compounds in which the alkyl group contains up to 6 carbon atoms will be found to be effective defoliant's, although some variation in effectiveness is to be expected. From the data in the following tables, it will be seen that the effectiveness may reach a maximum at say 3 or 4 carbon atoms and then decrease. However, there does not appear to be any critical or sharply defined upper limit to the number of carbon atoms in the alkyl group.

. There are known methods for the preparation ofsorne of these compounds. Others, however, are believed to be new, and methods for their preparation are illustrated in Examples 1, II, and III, following. H H

A general method for the preparation of trialky1 phosphorotrithioites (Formula 1, above) is disclosed in US.

Pate nt'No. 2,682,554. Triethyl, tripropyl, arid :tribu't'yl homologs were reported by Lippert Reid, Chem. Soc., 60, 2370 1938). These authors also slithcotton crop is to be picked mechanically they are also a 4 Arbuzov and Nikonorov, Doklady 62, 75 (1948).

One of the compounds of Formula 4 is also disclosed in the Kosolapoff reference, and a method of preparation is discussed by Tasker and Jones, J. Chem. Soc., 95, 1910 (1909). p

In all of the following examples, parts and percentages are by weight, unless otherwise indicated.

EXAMPLE I Preparation of S butyl 0,0-diphertyl phosphorathioite,

Formula 5 l 686.7 parts of PCl (40% excess) were placed in a 4-neck 'flask' fitted witha large addition funnel, stirrer, thermometer, andreflux condenser consisting of a Dewar condenser placed on top of a conventional water-cooled condenser. The vapor take-off from the Dewar condenser was connected to a water aspirator and a manometer, with a bleed to the atmosphere so that a partial vacuum could be maintained inthe reaction vessel. 564.7 parts of, phenol wereaddedthrough the addition funnel over a -minute period while the reaction mixture was subjected to 'constant'agitation, and while a partial vacuum Akad. Nauk, S.S.S.R.,

' was maintained in the reaction vessel to withdraw HCl vapors. Considerable'foaming and a temperature de' crease in the reaction'vessel indicated that HCl was being evolved. After phenol addition was completed, a heat ing mantle was applied to the reaction vessel and the temperature was slowly increased to 90 C. over a 6- hour period. The reaction mixture was allowed to stand overnight and then vacuum distilled. The fraction boil ing at 118-121" (2. at 0.4 mm. .pressure was collected as diphenyl phosphorochloridite, and approximately 265 parts were obtained. 1

90 parts of butyl mercaptan, 100 parts of triethyl amine, and 879 parts of benzene were placed in a 4-neck flask fitted with an addition funnel, stirrer, reflux condenser, and thermometer. 1919 parts of the diphenyl phosphorochloridite prepared above were added through marized known m'etho'ds row the preparation of these cointhe addition :funnel over a 30-minute period'while the reaction. mixture was subjected to constant agitation, and while the temperature was maintained with an ice'bath below "25 C. After ,chloridite addition was completed, the ice bath was removed and they reaction mixture was stirred for one hour at room temperature and allowed to stand overnight. Then the mixture was, stirred 'for four more hours, filtered, and the filtrate was stripped of solvent and excess amine and mercaptan. The stripped product was flash distilled under vacuum and the fraction boiling at 163 171 C.'at 0.10 mm. pressure was colleeted as S-butyl 0,0-diphenyl phosphorothioite; Apiproximately 128 parts of the .produetwere obtained.

nd 15736 d =1.1 55 fl erce'iit P: calculated: 10.1 1; routin 9.81 Percent S': calculated=f0.47; 'fou'nd=1'0.70

Preparation of O-4-'biphenylyl 'S,S-dipropyl 686.7-parts bigot, were iplaced in.-a 4-neck"flask1'fitted with-a large addition funnel, stirrer, thermometer, and reflux 'cond'enserconsisting of :a,-Dewa-r condenser placed on top :of 'a "conventional water cooled condehser. 850.9 of p pheriylphenol ':(*80'%- exces'sa, were added catalyst were added, and the mixture was refluxed intermittently for 16 more hours at 152166 C. The reaction m'urture was stripped of HCl and excess PCl for 3 hours at 35 C. under full aspirator vacuum. The

stripped product was vacuum distilled, and 527 parts of 4-biphenylyl phosphorodichloridite were obtained.

100 parts of propyl mercaptan, 150 parts of triethyl amine, and 879 parts of benzene were placed in a 4-neck flask fitted with an addition funnel, stirrer, reflux condenser, and thermometer. 135.5 parts of the 4-biphenyl I phosphorodichloridite prepared above were added through the addition funnel over a 30-minute period, while the while the temperature was maintained with an ice bath below 20 C. After dichloridite addition was completed, the ice bath was removed and the reaction mixture was stirred for 4.5 hours at room temperature and allowed to stand overnight. The mixture was filtered, and the filtrate stripped with a water aspirator and vacuum pump. Approximately 162.5 parts of O-4-biphenylyl S,S-dipropyl. phosphorodithioite were obtained.

Percent P: calculated=8.84; found=9.0l Percent S: calculated: 18.30; found: 18.02

EXAMPLE HI Preparation of dibutyl tolyl phosphorotrithioite Formula 7 2748 parts of PCl (100% excess) were placed in a 4-necl; flask fitted with a large addition funnel, stirrer,

thermometer, and Dry-Ice reflux condenser. 1804 parts of butyl mercaptan were added through the addition funnel over a period of 2 hours and 40 minutes while the reaction mixture was subjected to constant agitation, and while the temperature was maintained at 25 --35 C. After mercaptan addition was completed, the reaction mixture was allowed to stand overnight. The mixture was then stirred for one hour, heated at 6070 C. for 2 hours and 50 minutes, and stirred for 2 more hours at 25 mm. pressure to remove HCl and excess PCl The product was distilled, and the fraction boiling at 100- 127 C. at 0.14-0.17 mm. pressure was collected as S,S-. dibutyl phosphorodithiochloridite.

62.1 parts of mixed thiocresols, 100 parts of triethyl amine, and 879 parts of benzene were placed in a 4-neck flask fitted with an addition funnel, stirrer, reflux condenser, and thermometer. 122.4 parts of the S,S-dibutylphosphorodithiochloridite prepared above were added through the addition funnel over a -minute period while the reaction mixture was subjected to constant agitation, and while the temperature was maintained below C. with an ice bath. After dithiochloridite addition was completed, the ice bath was removed and the reaction mixture was stirred for 6 hours at room temperature and allowed to stand overnight. Then the mixture was stirred for one more hour, filtered, and the filtrate was stripped of solvent and excess amine with a water aspirator and vacuum pump. The stripped product was flash distilled under vacuum, and the fraction boiling at- 1 50167 C. at 0.10 mm. pressure was collected as 2o reaction mixture was subjected to constant agitation, and I dibutyl tolyl phosphorotrithioite. Approximately 170 parts of the crude product were obtained.

Percent P: calculated=9.3l; found=9.39 Percent S: calculated=28.93; found=29.58

The active ingredients for my defoliant compositions may be prepared by any of the methods referenced or described above. The appropriate alcohol, phenol, mercaptan or thiophenol need only be substituted into the reactions shown or referenced above.

.The following tables and examples summarize the defoliation activity of my compounds on cotton and other plants. Two standard test methods, the cotyledon test and the greenhouse spray test, were employed to determine defoliant activity on cotton, and these are described below.

Cotyledon test.Appr0ximately 30 days after planting, the test chemicals are applied to the cotyledons. By this time, the first and second true leaves have attained full size and the third and fourth are unfolding and expanding.

The chemicals are applied by dipping the cotyledons in a solution containing 500 p.p.m. of the compound. The solution is prepared by dissolving a Weighed portion of the test chemical in a small amount of a mixture of Atlox 3335 (25%) and xylene The emulsifier, Atlox 3335, is a commercial product, which comprises a mixture of alkyl aryl sulfonate blended with polyoxyethylene sorbitan esters of mixed fatty and resin acids. This emulsifiable concentrate is diluted with water to give the 500 ppm. concentration.

The amount of abscission is determined at 4 and 6 days following application, and is expressed as percent abscissed of the original number of cotyledons tested.

Greenhouse spray test-Cotton plants approximately 2-3 months old are chosen for treatment. By this time,

,the plants have obtained maximum growth before stunting due to pot size occurs.

The test chemicals are applied by spraying the plants with solutions containing 500, 1000, 1250, 2000, 2500, and/ or 5000 ppm. of the compound. The solutions are prepared by dissolving a weighed portion of the compound in a small amount of a mixture of Atlox 3335 (25%) and xylene (75 These emulsifiable concentrates are then diluted with water to give the required concentrations.

The results are taken 7 days after treatment. The number of leaves which drop is compared with the total number of leaves originally on the plant to give a percent defoliation rating.

Since the above described tests were performed on the compounds in the tables below in the greenhouse during the Winter, erratic results were often obtained. Wide variations in temperature, amount of sunlight, and other conditions necessitated the use of a control with which the activity of the test compounds could be compared. Therefore, in Tables I, II, and III, the results are based on one of my compounds, tributyl phosphorotrithioite, which had previously been thoroughly evaluated and field tested. By this I mean that the amount of defoliation shown by tributyl phosphorotrithioite in the cotyledon and spray tests was set equal to and all the other compounds were rated in comparison to it. Complete field test results on tributyl phosphorotrithioite showing its defoliant activity, are given in Example IV and Table V.

Table I includes data on the defoliant activity of my phosphorothioite compounds, as determined by the above described cotyledon test. This test is normally employed as a preliminary evaluation, and compounds showing defoliation comparable to the known control are retested in the greenhouse spray test.

Generic Formula P18); Fagmma (4) (A-VIOMPSR, Fomiula 5 giisfi, Formula (5) HSPISRE, Formula (7 Table II sllbws the results of the preliminary gi''enhpuse s ray test on the most promising compounds 'in Table I. Iii this sofid screening, the threshold concentratlon of 500 p.p.fn. is used; and the'cmpdunds Wlfih show gocid'act'ivity at [his 10W concentration are retested at awide range of concentrations. TABLE II.GREENHOUSE SPRAY TEST"SCREENI-NG RESULTS Percent Dfoliation, 500 p.p.m. Genetic Formula Structural Formula l Aftl 7 Days,

Based on Trl'butyl Phosphorotrithioite P['SCH2CH(CH3)2]3 J?(SR)3, Formula 1 {3603117) (80mm 1 30mm, Formula (2 Rousing, Fqrmula (a;

P (SAr)3, Formulg. (4); (Ai-OhPSR, Formula (5) The compounds showing the best activity in the screening test were retested at higher concentrations in the greenhouse spray test, and the results are reported in Table 111. As in Tables I and H, the data in Table III is based on the activity of tributyl phosphorotrithioite.

19 positions in this manner has enhanced the defoliating efiectiveness of the prior art compositions. It would be impractical to list here all of the possible combinations of my phosphorothioites with known defoliants, but such compositions should be considered within the scope of my invention.

TABLE III.GREENHOUSE SPRAY TESTRETEST RESULTS Percent Defoliation After 7 Days, Based on Tributyl Phosphorotrithiolte Generic Formula Structural Formula 500 1,000 1, 250 2,000 2, 500' 5, 000 p.p.m. p.p.m. p.p.m. p.p.m. ppm. p.p.m

F (501191 5. P(SG2H5)3 5.4 34.8 70.0 P(SG3H1)a 1 37. 2 2 50. 0 73. 4 83. 1 78. 0 P(SR)3, Formula (1) P(SC5H11)a 1 93. 0 3 100. 0 74. 4 80. 0 76.0 P (S 06111: 10. 0 P[SC H2CH(CH3)211 102. 2 89. 3 84. 1 P603111 (SC4H9)2 75. 6 139. 7 114. 9 "a.--" ggilsnlilrzcH-iohl sodlou; 138. 0 58. 4 109. 2 61. 4 96 S 125 8 (Row SR, Formula (2 I f gggg lgggg 87. 0 s9. 5 100. 3 9a. a 156. 6 as. 5 HOP (S C4H9)2 107. 1 120. 1 BOP Fmmula (3) (3311101 s 04m 64.0 62.6 67.7 48. 1 90. 5 61. 4 172. 5 3 186. 0 96. 0 137. 3 113. 0 185. 5 111. 1 120. 2 61. 5 A10P(SR)2, Formula (6) 66. 1 113. 0 120. 9

153. 1 119. 3 67. 6 102. 0 78. 6 91. 6 51. 1 178. 2 125. 1 ArSP(SR)2, Formula (7) 131. 1 110. 8

1 Tested at 312 p.p.m. 3 Tested at 625 p.p.m.

In the foregoing tables, my compounds were used alone, or, in one instance, two were mixed together and tested. However, these phosphorothioites may also 35.

be used in conjunction with other defoliant compositions of the prior art, such as aminotriazole, as shownin Table IV. In some applications the use of my com- TABLE IV.MIXTURES OF TRIPROPYL PHOSPHORO- 4O TRITHIOITE, FORMULA 1, AND AMINOTRIAZOLE Tripropyl Amino- Percent Defoliation 1 Phosphorotriazole, trithioite, lbs/acre lbs/acre 5-6 Days -15 Days 1 Average of three replicates.

Example IV, below, describes the field tests of two of my compounds on cotton, and summarizes the results obtained. One of, the compounds is tributyl phosphorotrithioite, which was used as a control in Tables I, II, and III.

EXAMPLE IV Field tests of tripropyl phosphorotrithioite artd tributyl phosphorotrithioite, Formula 1 TABLE V.-FIELD TEST RESULTS OF TRIPROPYL PHOSPHOROTRITHIOITE AND TRIBUTYL PHOSPHOROTRITHIOITE Concentration, lbs/acre Days State After 1.0 1.5 2.0 2.5 3.0 4.0 6.0

Application Tri- Tri- Tri- Tri- Tri- Tri- Tri- Trl- Tn'. 'In- Tri- Tri- Tri- Tripropyl butyl propyl butyl propyl butyl propyl butyl propyl butyl propyl butyl propyl butyl Arizona, percent defoliation 6 80 80 90 85 Do 13 85 90 95 95 California, percent defoliation varied 85-90 85-95 90-95 Louisiana, percent defoliation 6 71 86 76 76 76 12 69 83 80 83 86 5 -80 I 6 85 85-90 -85 7 93 88 Do 10 90-95 Oklahoma, percent v defoliation. 7 79 84 80 South Carolina,

percent defoliation 7 90 88 92 90 Texas, percent defoliation 8 53 26 86-90 92-97 88-93 91-94 97 97 compounds exhibit at least some degree of defoliatidn activity. Even those compounds which show low activity in the cotyledon test, based on a known defoliant, would be successful in the field if applied at sufficient concentrations. v V i p The same reasoning ifs applica ble inconsidering the 'activity of the phosphorothioite compounds of my invention on other plants.

D s given in E p Y, 1,. and VH, following, on the defoliation activity of tributyl phosphorotrithioite on other plants, "and it is obvious from the results-obtained on'cottonthat any of my eompounds would show comparable activity on these other plants. 7

Example V describes the field test on one variety of.

roses. Actually, 90 varieties were tested, and very good overall defoliation activity was obtained. The varieties tested are as follows:

Spectacular Ch n 11 Climbing Showgirl White Knight Cecile Brunner Starlet The Doctor Circus Ruby Lips Carousel Duet Helen Traubel Forward March Eclipse Isobel Harkness iiir'andy secpng Love Capistrano Pink Peace First Love 'Pocaho'nta's Countess Vandal Last chance Forty Niner Frau Karl Druschki Chief Seattle K. T. Marshall Fred Howard Roun'delay enemy Cricket Tiffany Etoile dHollande Fllml'dorfl Picture Briarclifl Dianty Bess Louis Philippe La Jolla County Fair Betty Prior Coral Queen F'rensham Dessan Gold Red Pinocchio Double Take Valentine 'iall Cerise Crimson Glory Dark First Love New Yorker Heat Wave Spartan Happiness w 7 Jacket: Golden Rapture No. '5 Fiimh Pink Rapture Climbing Crimson Glory Queen Elizabeth Pres. H. Hoover Stoplight Pink Champagne Better Times An emulsifiable concentrate was prepared containing 87% tributyl phosphorotrithioite, and the remainder oil and emulsifier. one gallon of this solution contained 7.6 lbs. of active ingredient. The solution was diluted with water to give emulsions containing 1 /2%, and 3% by volume of tributyl phosphorotrithioite.

12 These emulsions were sprayed on two-year old rose plants, at the rate of approximately 150 gallons per acre. At all concentrations, one hundred percent defoliation was realized' on the Queen Elizabeth variety after ap proximately two weeks. 5

EXAMPLE VI "Deyolimion activity of tributyl .phosphorotrithioite, Formula 1, on hydrangeas a An' emulsifiable concentrate was prepared containing tributyl phosphorotrithioite, and the remainder oil and emulsifier. The solution was diluted with water to give emulsions containing 1.0%, 1.5%, and 2.0% by volume of tributyl phosphorotrithioite. These emulsions were sprayed on'th'e Hamburg and Europa varieties of hydrangea, and -99% defoliation was noted after eight days.

EXAMPLE VII Defolia'tio'n activity of tributyl phosphorotrithioite, Formula 1, on trees An emulsifiable concentrate, prepared as in Example V, and containing 7.6 lbs. of tributyl phosphorotrithioite per gallon, was diluted with water to give emulsions containing /2 1%, and 2% by volume of the active ingredient. These emulsions were sprayed on Siberian elm, pear, sand cherry, and ash trees, and results were taken nine days after treatment.

Percent Defoli'ation Concentration Siberian Pear sand Ash Elm Cherry and good defoliation results were obtained at concentrations of by volume of tributyl phosphorotrithioite.

The results in Examples V, VI, and VII indicate that my compounds would bfe useful'on any plants which defoliate naturally or which are normally artificially defoliated.

I claim: v

-l. A method of defoliating living plants having an annual leaf-drop, which comprises applying to the leaves thereof in an amount sulficient to effect defoliation, a phosphorothioite corresponding to the formula RX-lL-XR wherein X is a member selected from the group consist ing of oxygen "and Sillflll' atoms, at least ofi 6f the mem bers X being a sulfur atom and R is a member selected from the group consisting of hydrogen, lower, alkyl, ben-zyl, phenyl, biphenylyl,nitrosubstituted phenyl, and alkyl-substi'tuted phenyl wherein said alkyl contains from 1 to 8 carbon atoms.

2. A method of defoliating living plants having an annual leaf-drop, which comprises applying to the leaves thereof in an amount suflicient to eflect defoliation, a trialkyl phosphorotrithioite wherein the alkyl groups are lower alkyl.

3. A method of defoliating living plants having an annual leaf-drop, which comprises applying to the leaves thereof in an amount sufiicient to effect defoliation, tri butyl phosphorotrithioite.

4. A method of defoliating cotton, which comprises applying thereto when the plant contains bolls, in an amount sufiicient to effect defoliation, a phosphorot hioite corresponding to the formula Similar tests were performed on plum and peach trees,

13 wherein X is a member selected from the group consisting of oxygen and sulfur atoms, at least one of the members X being a sulfur atom and R is a member selected from the group consisting of hydrogen, lower alkyl, benzyl, phenyl, biphenylyl, nitrosubstituted phenyl, and alkyl-substituted phenyl wherein said alkyl contains from 1 to '8 carbon atoms.

5. A method of defoliating cotton which comprises applying thereto when the plant contains bolls, in an amount sufiicient to etfect defoliation, a trialkyl phosphorotrithioite wherein the alkyl groups are lower alkyl.

6. The method of defoliating cotton which comprises applying thereto when the plant contains bolls, in an amount efiective to defoliate the cotton, tributyl phosphorotrithioite.

7. The method of defoliating cotton which comprises applying thereto when the plant contains bolls, in an amount efl'ective to defoliate the cotton, propyl dibutyi V phosphorotrithioite.

8. The method of defoliating cotton which comprises applying thereto when the plant contains bolls, in an amount effective to defoliate the cotton, S, S dibutyl phosphorodithioite.

9. The method of defoliating cotton which comprises applying thereto When the plant contains bolls, in an amount effective to defoliate the cotton, S-propyl S-butyl O-methylphenyl phosphorodithioite.

10. The method of defoliating cotton which comprises applying thereto when the plant contains bolls, in an amount efiective to defoliate the cotton, dibutyl dimethylphenyl phosphorotrithioite.

No references cited. 

1. A METHOD OF DEFOILATING LIVING PLANTS HAVING AN ANNUAL LEAF-DROP, WHICH COMPRISES APPLYING TO THE LEAVES THEREOF IN AN AMOUNT SUFFICIENT TO EFFECT DEFOLIATION, A PHOSPHOROTHIOTE CORRESPONDING TO THE FORMULA 